Condensation product and method



Patented Mar. 10, 1942 I UNITED STATES PATENT OFFICE CONDENSATION mixerANDMETHCD v Edwin T. Clocker, Bethlehem, Pa.

No Drawing. Application April es, 1939, 7 Serial No. 270,651 r 20Claims. (Cl. 26022) My invention relates to methods of producing animproved condensation product suitable for use in resins, lacquers,paints, varnishes, enamels, plastic masses, and for other similarpurposes, and to the new product so produced. This application is acontinuation in part of my co pending applications, Serial No. 165,898,filed September 27, 1937 for Condensation product and method, Patent No.2,188,885, and Serial No. 165,900, filed September 27, 1937 for Coatingcomposition and method, Patent No. 2,188,884, since it contains claimsdivided from said applications. Serial Nos. 165,898 and 165,900 are inturn continuations in part of my copending applications Serial No.759,086, filed December 24, 1934, Patent No. 2,188,882, and Serial No.117,243, filed December 22, 1936, Patent No. 2,188,883,

both for Condensation product and method- Patent No. 2,188,882, includesthe generic claims and certain species relating to the condensation ofan acyclic olefinic acid having less than ten iiig from ten totwenty-four carbon atoms in its carbon chain.

A further purpose is'to produce polyhydric alcohol esters ofcondensation products formed by condensation of a condensable ethylenetype, acidic compound having less than ten carbon atoms in its carbonchain at the carbon chain of a nonconjugated unsaturated nonhydroxylatedfatty ester or the like by suitable application of heat and, desirably,also pressure. A temperasubstantial condensation. .Very good results areobtained using temperatures, of at least 150 C. and in excess of theordinary boiling point of the acyclic olefinic acid withreturncondensation.

carbon atoms in the carbon chain, or its ester,

Patent No. 2,188,884 is concerned paroil acids and to esterify thecondensation prod- Serial No. 231,760, filed September 26, 1938, for

Condensation product and method, Patent No. 2,188,886, is directed towater insoluble metallic salts. SerialNo. 231,761, filed Sept. 26, 1938,for Oily dispersion material, Patent No. 2,188,887, relates to oils,fats and waxes emulsified by the condensation product of the invention.Serial No. 235,252, filed October 15, 1938, for Condensation product andmethod, Patent No. 2,188,888, is directed to condensation with oleicacid and its compounds.

A further purpose is to cause the condensation to take place between onemolecular equivalent of condensable ethylene type acidic compound havingless than ten carbon atoms in its carbon chain and one molecularequivalent of noncon- -jugated unsaturated nonhydroxylated carbon chainester having from ten to twenty-four atoms in the carbon chain. I

A further purpose is to produce a polyhydric alcohol ester of an acylicolefinic acid or the like having less than ten carbon atoms in itscarbon chain, partially or completely saturating the double bonds of anonconjugated unsaturated nonhydroxylated, fatty oil or the like, Afurther purpose is to condense maleic anhydride or the like with adrying oil such as linseed oil or with drying oil acids such as linseeduct with a polyhydric alcohol. v

A further purpose is to produce an acid polyhydric alcohol ester of mynovel condensation product, and either to leave the remaining acidicvgroups unsatisfied, or to cause them to combine with basicmaterials'such as drier metals, basic dyestufls and other'basiccompounds.

A further purposeis to cause the acid group I of a condensation productof an acyclic olefinic A purpose of my invention isto produce polyhydricalcohol esters of a condensation product resulting from condensationbetween an acyclic olefinic acid having less than ten carbon atoms inits carbon chain and a nonhydroxylated ester of a nonconjugatedunsaturated nonhydroxylated aliphatic acid having from ten to twentyfourcarbon atoms in its carbon chain. Any

relatively short chain compound containing the ethylene linkage incondensable form may be condensed with any nonconjugated' unsaturatednonhydroxylated aliphatic ester or the like hav-' acid or acid anhydridehaving less than ten car.- bon atoms in its carbon chain with a nonconjugated unsaturated nonhydroxylated fatty oil or the like having from tento twenty-four carbon atoms in its carbon chain to react with apolyhydric alcohol.

A. further purpose: is to cause the condensation product of an acyclicolefinic acid having less than ten carbon atoms in its carbon chain anda nonconjugated unsaturated nonhydroxyb ated aliphatic ester having fromten .to twentyfour carbon atoms in its carbon chain, preferably heatingthe ingredients to varnish viscosity and thinning with a suitablesolvent to produce a varnish.

A further purpose is to cause cellulose in soluble form, preferably as acellulose ether (for example ethyl cellulose, methyl cellulose or thelike) to combine with the novel acidic condensation product of thepresent invention to produce an ester of the acidic condensationproduct. Cellulose is of course a polyhydric alcohol, the ether groupbeing inert throughout the reaction but desirable as rendering thematerial soluble.

Further purposes appear in the specification and in the claims.

It has been known for some time that maleic anhydride or substancesyielding maleic anhy-' dride will condense with carbon chain compoundscontaining a conjugated system of double bonds. For example, 'Morrell,Marks and Samuels in British Patent No. 407,957 disclose a condensationof maleic anhydride with tung oil, a conjugated compound.

-I have discovered that, under suitable conditions, maleic anhydride andcompounds which behave similarly, as discussed below, will react withnonconjugated unsaturated nonhydroxylated fatty oils and similarcompounds having fromten to twenty-four carbon atoms in the carbon chainand the condensation product thus obtained may be formed into polyhydricalcohol esters. v

{To produce the maleic condensation product, the maleic grouping must bepresent in condensable form, preferably as maleic anhydride.

The condensation is of course obtained from any of the compounds whichyield maleic anhydride and the like, such as malic acid, fumaric acid,

maleic acids having less than ten carbon atoms in their carbon chains,and other equivalents.

Wherever I refer herein to an acid or to an acid group, I of courseinclude an acid anhydride and an acid anhydride group, and vice versa.Wherever I refer to an ester, I include also a half ester.

Investigation of a large number of compounds has shown that condensationwith an ester of a phatic acid having from ten to twenty-four carbonatomsin the carbon chain is generally char- 1 acteristic of chaincompdupds having the ethylene linkage and having less than ten carbonatoms in the carbon chains, which are substituted on one or both sidesof the double bond to form acids or acidanhydri'des, or 'half estersthereof, or similar compounds. These compounds are oleflnic as they areacyclic and have .the ethylene linkage; Such 'olefinic compounds aremonosubstituted when they contain only one acid, acid anhydride oresterified group; for example crotonic acid. Such olefinic compounds aredi-substituted when they contain two acid, acid anhydride or esterifiedgroups; for example maleic anhydride, citraconic anhydride, maleic acid,acid methyl maleate.

When an olefinic compound of less than ten the ethylene linkage incondensable form, the expression in condensable form, is intended toindicate that the compound is not a hydrocarbon, for example, but thatit is an acid or-acid an-. hydride; or half esterthereof, or a similarcompound which will condense with a nonconiugated unsaturatednonhydroxylated fatty acid or the like having from ten to twenty-fourcarbon atoms in the carbon chain.

The longer the carbon chain of the acyclic oleflnic acid or acidanhydride, or half ester thereof, or similar compound, the less vigorousis As explained herein, in order to avoid a mere esterification ofalcohol groups in the initial reaction,'as distinguished from acondensation atthe double bond, the oil or similar compound should benonhydroxylated. Where necessary, precautions should be used to avoidhydroxylation by hydrolysis or otherwise. As well known in the art, inorder to prevent or minimize hydrolysis, the reacting components shouldbe reasonably dry, and water formed by decomposition of a reactingingredient during the reaction should be removed. For example, if maleicacid (as distinguished from the anhydride) is caused to react with anoil or similar compound, it is preferable to use a relatively hightemperature to cause rapid reaction, and it is preferable to permitelimination of the water formed by decomposition of the maleic acid intomaleic anhydride, as by permitting distillation and avoiding refluxing.Where maleic anhydride or a similar compound not producing water bydecomposition isj to be used, the desirability cf avoiding refluxing ofcourse ceases.

Wherever reference is made herein to maleic anhydride, it'will beunderstood thatI include substances wliichfyield maleic anhydride ifsubjected to the conditions at which maleic anhychain. In the case ofany ester of any oleflniccompound, the carbon chain of the oleflniccompound should have less than ten carbon atoms, the carbon chain of thecompound added by esterification not being counted.

In all cases where I refer in the specification -toless than ten carbonatoms in the carbon .chain of the acyclic oleflnic compound, it will .beunderstood that a more vigorous reaction is obtained with compoundshaving less than seven.

twenty-four carbon atoms. in the carbon chain,-

will result in esterification between the acidic group of maleic ahydride and the hydroxyl h roup or groups in the ester of the aliphaticacid. Condensation betweenthe maleic anhydrlde or the like and thecarbon chain of the ester of the hydroxylated aliphatic acid, will onlytake place after esteriflcation is; complete, and in case maleicanhydride .or the like in excess of that consumed by the esterificationis present in contact with the ester of the hydroxylated aliphatic acidunder the proper conditions.

The esterification of course produces a change inproperties, and thecondensation product of an ester of a hydroxylated aliphatic acid can 1in general be given properties comparable with those of the condensationproduct of an ester of a'nonhydroxylated aliphatic acid, only bydestroying thefesterification of the maleic anhydride or the like, as byhydrolysis.

Due to the difiiculty in obtaining a condensation reaction betweenmaleic anhydride or the like and an ester of a nonconjngated unsaturatedhydroxylated aliphatic acid having from ten to twenty-four carbon atomsin the carbon chain, due to the change inproperties caused byesteriflcation, and due to the difficulty of decomposing the ester, theclaims have generally been drawn to exclude hydroxylated aliphaticesters. This means that such esters are not 'sufflciently hydroxylatedto interfere with the condensation by esteriflcation. Oils which arep'olymerized by blowing with air are usually hydroxylated. I I

In those cases where the claims do not exsuggest. oleic, linoleic,linolenic, clupanodonic stood that esters of mixtures of yarious fattyclude hydroxylated aliphatic esters, it will beg understood that morethan mere esteriflcation at the hydroxyl group is intended-there shouldbe condensation at a point of unsaturation on the carbon chain of theester.

When reference is made to the maieic grouping in condensable form,it'will be understood that it is intended to designate'maleic anhydride,a substance yielding maleic anhydride or a similar compound which iscapable of condensing to enter the carbon chain of a nonconjugatedunsaturated nonhydroxylated aliphatic compound having from' ten totwenty-four carbon atoms in the carbon chain. A maieic condensationproduct may be obtained from any such compound having the maieicgrouping, preferably maleic anhydride.

As will later be explained in considerable detail, the presence of theacid or acid anhydride radical in the condensation product is distinctlyadvantageous, because of the reactions of which the acid or acidanhydride radical is; capable and the uses to which such reactions maybe put. 4

A wide variety of nonconjugated unsaturated nonhydroxylated ca'rbonchain compounds having from ten to twenty-four carbon atoms in thecarbon chain may be employed. Esters of fatty acids with mono-, diorpoly-hydric alcohols, for example .glyceryl or glycol esters, areparticularly desirable,

tween'180 C. and 260 C.) and .preferably also Where referenceflis madeto the length of the carbon chain as being from ten to twenty-fourcarbon atoms, it is 'intended to include com-' pounds having ten -carbonatoms, twenty-four carbon atoms or any intermediate number of carbonatoms in the. chain. The reference to the length of the carbon chainapplies to the carbon chain of the acid/ ad, glyceride, for example.contains three such carf-bon chains united to a glyceryl group.

As examples of the'type of nonconjugated unsaturated nonhydroxylatedaliphatic acids having from ten to twenty-four carbon atoms in thecarbon chain whosefestersI may uselI acids, or of various esters, or ofthe esters and the free fatty acids, may be employed if desired The oilsabove referred to may generally be ,described as oils predominantlyconsisting of glycerides of linoleic and oleic acids.

When I refer to the grouping of a nonconjugated unsaturatednonhydroxylated aliphatic acid having from ten to twenty-four carbonatoms in the carbon chain, I mean to include the esters of the acid,whether with mono-, dior poly-hydric-alcohols. I do not include herein.hydroxylated aliphatic oils, etc., because, while the condensation ofmy invention may ,in certain cases be obtained with them, specialprecautionsmust be' taken because of the tendency of,hydroxylated fattyoils, etc., to esterify and gel. Typical hydroxylated fatty oils arecastor Oil and cashew nut shell oil."

In the condensation, I may desirably employ one molecular equivalent ofnonconjugated unsaturated nonhydroxylated aliphatic ester or the like toone molecular equivalent of acyclic oleflnic acid and subject themixture to a temperature of between C.a1id 300 C, (more desirably be-'to high pressure to facilitate the reaction. The temperature may in somecases be somewhat above 300 C. if the reacting components can stand'such high temperature. The reaction will desirably proceed for a timeof at least threequarters of an hour and suflicient to producesubstantial condensation; Verygood results are and in excess of theordinary boiling point of the acyclic oleflnic acid with returncondensation. Pressure may desirably be applied by simply confining thereaction components between the walls of some vessel such as a pressureautoclave and then heating the reaction components. Pressure may also beapplied in any other suitable way, as by pumping the reaction componentsinto the vessel or introducing an inert gas under pressure. I have usedpressures up to 300 pounds per square inch with success. Of course thedesirable pressure will vary with the individual reaction. When I referherein to reaction under retuni condensation I mean to include not onlyreaction in the confining walls of a pressure autoclave as in Example 1but also under reflux as in Example 2.

A suitable catalyst may, be used to accelerate the reaction and toincrease the yield. I do .not, however, iind that a catalyst isnecessary.

The-condensation reaction-may be carried out in the presence ofsuitablesolvents, although this isnot usually necessary.

In ordinary practice I prefer notto use suflicient acyclic olefinicacid, haying less than ten carbon atoms in the carbon chain, to saturateall of the doublebonds in the fattyoil, etc., having/fromten totwenty-four ,earbon atoms in the carbom chain. The con tfeifiatioh'product thusordinarily has an iodine value.Generally the autoclave.

it'is suflicient to saturate one-sixth to one-third cit-the double bondsin the fatty oil, etc? Thus in olive oil one-third of the double bonds(one) is Ordinarily saturated, and in linseed oil onesixth (one). But inindividual cases it may be desirable to saturate more ethylene linkagesin the fatty oil, and even to completely saturate with polyhydricalcohols to produce a resin as in the case of the condensation productsof the other examples.

My novel condensation product may be made 5 with nongoniugatedunsaturated nonhydroxylatthem. To saturate all of the ethylene linkagesin the way in which my initial condensation product is obtained;

Exmnr: 1

In a pressure autoclave, 180 parts by weight of alkali-refined linseedoil are mixed with 20 parts by weight of maleic anhydride. 'lI'hetemperature is maintained at from 230 C. to 260 C.

some extent, dependent upon the character 01.

ed drying, semidrying or nondrying fatty oils having from ten totwenty-four carbon atoms in the carbon chain, or mixtures of the same,and the characteristics of the product are, to

the oils or the like employed in the reaction. For convenience, thegroup of semid y s oils is classed with the group of drying oils in theclaims, so that a claim for a drying oil ,will include a semidrying oil.When nonconjugated unsaturat ed nonhydroxylated drying. oils are causedto react with maleic anhydride or the like, the products dry in the airat ordinary temperatures to form hard dry films whether or not driersare used. Likewise, the condensation products of for one hour, apressure of about 30 pounds per square inch developing. The reaction maybe ob-..

tained satisfactorily at 150 0., but is much slower at this lowtemperature, and the temperature may be raised to as much as 300 C. oreven somewhat higher, but a high temperature may nonconjugatedunsaturated nonhydroxylated drying oils generally exhibitthermo-hardening properties, being convertible at 70 C. to 80 C., forexample into hard resistant varnish-like films in'short periods of time.Where nonconjugated cause some difllculty due to carbonization. Aftercooling, the reaction product is removed from 'The condensation productis slightly darker and more viscous than the original linseed oil. It issoluble in acetone, ethylacetate, ether, xylene, carbon tetrachloride,higher petroleum hydroca bone and turpentine;

and semi-soluble in 95% e hyl alcohol. The con-- densation product ismiscible with fatty oils and solutions of cellulose derivatives such asnitro- To 180 parts by weight of nnseea oil are added 25 parts by weightof citraconic anhydride (an 45 or xylene.

alkyl-substituted maleic anhydride) and the mixture is heated in athree-neck flask, equipp with a reflux condenser, at about 250 C. forabout threes-quarters of an hour. 'At. the end of this period, nofurther citraconic anhydride appears to condense under the reflux,indicating completion, of the reaction. As a precaution, heating iscontinued for about 15 minutes longer.

. The reaction product is less viscous than the maleic condensationproduct of linseed oil ob- ,tained in Example 1, but has the sameproperties otherwise. P

' EXAMPLE 3 a f A mixture of 25 parts by weight of linseed oil and 2.4parts by weight of crotonic acid (an v acyclic. oleflnic acid) areheated under pressure at about 250 C. for about two hours. Theconunsaturated nonhydroxylated semidrying oils such as sunflower, soya,sailiower, and other similar oils are caused to react with maleicanhydride or the like, the condensation products do not dry so readilyas the condensation products obtained from the drying oils. An exampleof the drying behavior of the condensation product obtained by Example 1is as follows:

YEMEN-E5) A 1:1 xylene solution of the reaction product obtained inExample 1 to which soluble driers are added to the extent of 0.03% ofcobalt, 0.115%

of manganese and 0.5% of lead, for example in 40 the form of linoleatesor resinates, dries to a hard film at room temperature in about fivehours and may be stoved to a hard film at 80 C. in about one andone-half hours. The film produced is not acted upon by water, ethylalcohol, ben'zine',

. Without limiting myself to any exact struce ture for the condensationproduct, it would appear that the condensation product is an addition,product at a double bond in the carbon chain of the nonconjugatedunsaturated nonhye droxylated fatty ester or the like to the con-'densable oleflnic compound or the like. For ex-' ample, ifli'nolenic'ester reacts with maleic anhydride, the first stage in thereaction appears to be in general as follows (the acid only being shownan?! not the glyceride). Of course if enough-ma eic anhydride bepresent, the same reaction will take place at each double bond in thelinolenic ester.

densation product has similar properties to the maleic-linseed oilcondensation product obtained in Example 1' as respects solubility abovenoted, and dispersing power, drying action and adherence to metals,noted below. i g y Exmu: 1 A mixture of 900 parts by weight of linseedoil and 1'12 parts by weight of acid methyl maleate (a maleic halfester). ,are heated under pressure at about 250 'C. forrabout- 2'hours.The condensation product, although less acidic than the Linolenic acid aMaleic anhydrlde CHQCHKJHTCHCHQCH=CHCH1CH=GH(CH1)1COOH Maleiccondensation product of linolenic acid It will, of course, be evidentthat three of these fatty acid chains will be combined to the glycerylproduct of Examples; 1 to .2, may beest nn qn radicalin each molecule of'oil. 1 H

. 2,275,843 The iodine value of the condensation product acterized bythe linkage:

x-d c-r-c oz where X and vY are carbon chains without conjugated doublebonds and Z is a hydrogen atom, a

metal or an ester group.

The reaction above will be modified in well known manner it the ester ofsome other nonconjugated unsaturated nonhydroxylated aliphatic acidhaving between ten and twenty-four carbon atoms in the carbon chain beemployed or if some other olefinic acid having less than ten carbonatoms in its carbon chain,- be used instead of or in mixture with maleicanhydride.

, -.When maleic acid or a substance yielding maleic acid is condensedwith a nonconjugated unsaturated nonhydroxylated fatty oil or the like,it appears to change to maleic anhydride and the maleic anhydridecondensation product results.

I Esters Esterification of the acid group is frequently desirable. Thealcohol used may be either aliphatic or aromatic and either monoorpolyhydric. Where the term poly-hydric is used, di-hydric is included,so thatglycol is a polyhydric alcohol Just as much as glycerine orcellu-..

lose.

Due to their ability to form esters of high molecular weight,esterification with poly-hydric alcohols' is particularly desirable, andthis subject matter is accordingly being stressed in the pres-- entapplication. The esters of the condensation product with poly-hydricalcohols'have interesting and imusual properties as noted below. Thepoly-hydric alcohol ester of the condensation shorter time than thatrequired for linseed oil and, when stoved at 80 C., gives a hard filminabout one and one-half hours. The film is not attacked by water,alcohol'or xylene.

In Example 6 the esterificationis all at the acidic groups of the maleicanhydride.

Glycerine may very desirably be employed for esterifying thecondensation product of the presproduct of maleic anhydride or the likewith a nonconjugated unsaturated nonhydroxylated fatty drying oilexhibits the same desirable airdrying and thermo-hardening properties asthe unesterified condensation product, and may-be used for paint,varnish and lacquer work with success.-

The following example describes the prepara. tion oi. the glycol esterof the acyclic olefinic acid fatty oil condensation product.

EXAMPLE 6 ample 1, are mixed with 1.6 parts by weight of ent invention,and very desirable varnish resins having useful drying properties may bemanufactured by esterifying with glycerine. The acid number willdesirably be reduced to about 20 to 30 by the glycerine esterification.The resulting product has solventfiiroperties and may be incorporatedwith other resins, such as rosin. This mixture may be heated to therequired varnish viscosity and then thinned with a common forganicsolvent such as. a benzene hydrocarbon (benzene, toluene, xylene, etc.)or butyl alcohol. These results may be obtained by esterifying thecondensation product of a nonconjugated unsaturated nonhydroxylateddrying oil or the drying oil acids.

EXAMPLE 7 I Heat together parts by weight of the maleic anhydridecondensation product of linseed oil as obtained in Example 1, and 11parts by weight of glycerine at 230 C. until a drop of the reactionmixture remains clear on cold metal. Then add to the reaction mixture 60parts by weight of wood rosin and heat at 285 C. for 45 minutes. Theproduct gives an acid number of 25 as compared with 113 for theacidnumber of the uncondensed mixture. e

This product, when cut with petroleum spirits containing drier, dries toa hard, water-resistant film.

Other suitable poly-hydric alcohols aside from glycol and glycerine maybe employed for esterification. Cellulose is an example of such a poly-'hydric alcohol. Ordinary cellulose is not soluble and for that reasondoes not react, but when cel-v lulose' is solubilized as by formingcellulose ether (ethylcellulose or methyl cellulose, etc.) it re- Up to20% of ethyl cellulose is dissolved in the maleic anhydride condensationproduct of linseed oil at about 220? C. A reaction occurs accompanied bythe splitting off of water. The reaction product is desirable as a metalcoating, drying to a tough hard film of high gloss, very hightransparency and great water resistance.

Other soluble forms of cellulose may be employed providing they willmeltwithout decomposition below' about 300 C. .Cellulose acetatedoesn'ot'meltat a low enough temperature to givethe above-reactionconveniently and cellulose nitrate "decomposes at the temperaturerequired.

ethylene glycol and the mixture is maintained at 70 about 180 'C. untilthe reaction ceases. A 1:1 xylene solution oi-"the reactionproduct,'when treated with a suitable quantity of metallic driers, asdescribed for instance in- Example 5, dries at In the caseof thesematerials solvents must be employed'in order to obtain esterification.

Therefis a class of poly-hydric alcohols which are also ethers. Typicalexamples of such polyhydric alcohols containing ether groups areethylene glycol monoethyl .ther (Cellosolv) diethylene glycol monoethylether (carbitol), and the 7 room temperature to. a-hard film in asomewhat 7 methyl, butyl, etc., ethers of the same.

Patent is:

. EXAIPLE 9 A mixture of 100 grams of the maleic anhydride condensationproduct of linseed oil obtained in Example 1 and 10 grams of ethyleneglycol monoethyl ether is heated to 180 C. and maintained at thattemperature until the reaction ceases. The resulting product isdesirably used as an ingredient of emulsions 7 Throughout thespecification and claims, where I refer to nonhydroxylated esters ofnonconjugated unsaturated nonhydroxylated aliphatic acids having fromtento twenty-four carbon atoms in the carbon chain, I mean such esters'asare unoxidized or nonpolymerized or not sufficiently oxidized orpolymerized to interfere with the reactions disclosed herein. Thus, inreferring to linseed oil, I mean the product generally known as such,raw or refined, and not linseed oil sufflciently oxidized or polymerizedto preventor seriously interfere with the formation of a condensationproduct at a double bond.

Many of the fish oils contain varying percentages of fatty alcohols,which will 'of course react with maleic anhydride to form esters. Theesterified fatty alcohols may be allowed to remain in the condensationproduct, or the alcohols may be removed before condensation takes place.

It will be evident that the condensation product of my invention may beoxidized subsequent to condensation; I

Where reference is made to poly-hydric alcohols, it is intended toinclude di-hydric alcohols. Reference to acids is intended toincludeacid anhydrides and half esters of acids. Reference to esters isintended to include partially complet ed esters such as half esters. v

It will be understood that the condensation of minute amounts of theolefinic compound with the nonconjugated unsaturated nonhydroxylatedfatty compound will not appreciably change the character of the latter.In general, at least 1% (based on the weight of the condensationproduct)of the olefinic compound should be combined with the nonconjugatedunsaturated nonhydroxylated fatty compound in the product to insure adistinctive character of the product;

In view of my invention and disclosure variations and modifications tomeet individual w or particular need will doubtless become evident tovothers skilled in the art, to obtain all or part of the benefits of myinvention without copying the exact process or productdescribed.

Having thus described my invention, what I claim as new and desire tosecure by Letters 1. The process" of forming a condensation productwhich comprises reacting an acyclic olefinic acid having less than tencarbon atoms in the 1 carbon chain with the' carbon chain of an oilpredominantly consisting of-glycerides of linoleic so and oleicacids ata temperature in excess of 150 l C. and for a time of at leastthree-quarters of I an hour, the reaction being substantially whollybetween. the acyclic oleflnic acid and the oil, and esterifying theacidic condensation product with a poly-hydric alcohol. I

'2. The process of producing a resin. or the like, whichcomprisesireacting an acyclic olefinic acid having less than ten carbonatoms in its carbon chain with a nonconjugated unsaturated non- 70.

hydroxylated fatty oil having from ten to twenty-four carbon atoms inthe carbon c aim of the fatty acids at a temperature-above the ordinaryboiling point of the acy lo oletlnic acid with return condensation thereaction being sub- ,stantially wholly between the acyclic ,oleflnicacid and the oil, and esterifying the acidic re actionproduct with apoly-hydric alcohol;

3. The process ofproducing a resin or the like, which comprisescondensing maleic anhydride with an oil predominantly consisting ofglycerides of linoleic and oleic acids at a temperature in excess of C.and for a time of at least the oil, and esterifying the acidiccondensation product with a poly-hydric alcohol.

4. The process of producing a resin or the like, which comprisesreacting maleic anhydride with an oil predominantly consisting ofglyceridesof linoleic and oleic acids at a temperature above theordinary boiling point of maleic anhydride the reaction beingsubstantiallywholly between the maleicanhydride'and the oil, andesterifying the acidic reaction product with a poly-hydric alcohol. f

5. The process of producing a resin or the like, which comprisescondensing an acyclic olefinic acid having less than ten carbon atoms in.its carbon chain at a point of unsaturation in'the carbon chain of anonconjugated unsaturated nonhydroxylated drying oil having from ten totwenty-four carbon atoms in the carbon chains .of the-fatty acids of theoil, at atemperature in excess of 150 C. and for a time of at leastthree- .quarters of an hour, the reaction being substantially whollybetween the acyclic oleflnic 'acid and the oil, and esterifying theacidic condensation product with a poly-hydric alcohol.

6. The process ofproducing a resin or the like, which comprisescondensing an acyclic olefinic acid having less than ten carbon atoms inthe carbon chain with a nonconjugated unsaturated nonhydroxylated fattyoil having fromten to" twenty-four carbon atoms inthe carbon chain ofthe fatty acids of the oil, at a temperature Iin excess of 150 C. andfor a timenf at'least threequarters of an hour, the reactionbeingsubstantially wholly between the acyclic oleflnic acid and the oil, andesterifying the acidic condensa--.

tion product with glycerine.

. I. The process of producingra resin, or thelike,

"wholly between the maleic anhydride and the oil, and esterifying theacidic condensation product with cellulose ether.

8. The process of producing a resin or the like,

which comprises condensing an acyclic oleflnicacid having less' than tencarbon atoms in the carbon chain with a nonconjug'ated unsaturatednonhydroxylated fatty oil having from ten to twenty-four carbon atoms inthe carbon chain of the fatty acidsmf the oil, at a temperature inexcess of 150 C. and for a time of at least three-quarters of an hour,.the reaction being substantially wholly between the acyclic olefinic.acid and the oil, and esterifying the acidic condensation product witha cellulose ether. I

9,. The process of producing a' resin or the like, which comprisescondensing an acyclic olefinic acid having less than ten carbon atoms inthe carbon chain with a nonconjugated unsaturated nonhydroxylated fattyoil having from' ten to twentyefour carbon atoms in the carbon chain -ofthe fatty acids of the oil, at a temperatiire in excess of 150 C. andfor 'a time of at leastthreequarters of an hour, the reactionbeing-"submits atoms in the carbon chains of the fatty acids of the oil,an acyclic olefinic acid having less than ten carbon atoms in its carbonchain, said acyclic olefinic acid at an intermediate point in its carbonchain being attached to an intermediate point in a carbon chain of afatty acid of the oil, with the acidic groups of the acyclicolefinicacid not satisfied by the oil, and a poly-hydric alcohol combined withan acidic group ofthe acyclic olefinic acid.

11. A condensation product consisting of an oil predominantly composedof glycerides of linoleic and oleic acids, an acyclic olefinic acidhaving less than ten carbon atoms in its carbon chain, said acyclicolefinic acidat an intermediate point in its carbon chain being attachedto an intermediate point in a carbon chain of a fatty acid of the oil,with the acidic groups of the acyclic olefinic acid not satisfied by theoil,

and a poly-hydric alcohol combined with an acidic group of the acyclicolefinic acid.

12. A condensation product consisting of an oil predominantly composedof glycerides of linoleic and oleic acids, maleic anhydride which at anintermediate point in its carbon chain is attached to an intermediatepoint in.a carbon chain of a fatty acid of the oil, with the acidicgroups of the maleic anhydride not satisfied bythe oil, and apoly-hydric alcohol combined with an acidic group of the maleicanhydride.

13. A condensation product consisting of an oil predominantly composedof glycerides of linoleic and oleic acids, maleic anhydride which at anintermediate point in its carbon chain is attached to an intermediatepoint in a carbon chain of a fatty acid of the oil, with the' acidicgroups of the maleic anhydride not satisfied by the oil, and celluloseether combined with an acidic group of the maleic anhydride.

14. A condensation product consisting of a non-conjugated unsaturated'non-hydroxylated' drying oil having from ten to twenty-four atoms inthe carbon chain of the fatty acids of the oil, an acyclic olefinic acidhaving less than ten carbon atoms in its carbon chain, said acyclicolefinic acid at an intermediate point in its carbon chain beingattached to an intermediate point in a carbon chain of a fatty acid ofthe oil, with the acidic groups of the acyclic olefinic acid notsatisfied by the oil, and a poly-hydric alcohol combined with an acidicgroup of the acyclic olefinic acid.

15. A condensation product consisting of a non-conjugated unsaturatednon-hydroxylated fatty oil having from ten to twenty-four carbon atomsin the carbon chain of the fatty acids of the oil, an acyclic olefinicacid having less than ten carbon atoms in its carbon chain, said acyclic7 olefinic acid at an intermediate point in its car'- bon chain beingattached to an intermediate point in a carbon chain of a fatty acid ofthe oil, with the acidic groups of the acyclic olefinic acid notsatisfied by the oil, and glycerine combined with an acidic group of.the acyclic olefinic acid.

16. A condensation product consisting of a non-conjugated. unsaturatednon-hydroxylated fatty oil having from ten .to twenty-four carbon atomsin the carbon chain of the fatty acids of the oil, an acyclic olefinicacid having less than ten carbon atoms in its carbon chain, said acyclicolefinic acid at an intermediate point in its car-.

bon chain being attached to an intermediate point in a carbon chain of afatty acidof the oil, with th acidic groups of the acyclic olefinic acidno satisfied by the oil, and cellulose ether combined with an acidicgroup, of the acyclic olefinic acid. I

17. A condensation product consisting of a non-conjugated unsaturatednon-hydroxylated fatty oil having from ten to twenty-four carbon atomsin the carbon chain of the fatty acids ,of the oil, an acyclic olefinicacid having less than ten carbon atoms in its carbonchain, said acyclicolefinic acid at an intermediate point in its carbon chain beingattached to an intermediate point in a carbon chain of a fatty acid ofthe oil, with the acidic groups of the acyclic olefinic acid notsatisfied by the oil, and a poly-hydric alcohol containing an .ethergroup combined with an acidic group of the acyclic olefinic acid.

18. A condensation product consisting of linseed oil, an acyclicolefinic acid having less than ten carbon atoms in its carbon chain,said acyclic olefinic acid at an intermediate point in its carbon chainbeing attached to an intermediate point in a carbon chain of a fattyacid of the oil, with the acidic groups of the acyclic olefinic acid notsatisfied by the oil, and a poly-hydric alcohol combined with an' acidicgroup of, the acyclic olefinic acid.

19. A condensation product consisting of .lin-

20. A varnish or the like comprising a condensation product consistingof a drying oil predominantly composed of glycerides of linoleic andoleic acids, an acyclic olefinic acid having less than ten carbon atomsin its carbon chain, said acyclic olefinic acid at an intermediate pointin its carbon chain being attached to an intermediate point in a carbonchain of a fatty acid of the oil, with the acidic groups of the acyclicolefinic acid not satisfied by the oil, and a polyhydric alcoholcombined with an acidic group of the acyclic olefinic acid.

EDWIN T. CLOCKER.

